NOTES
2928
crystalline product had a melting point of 151-153' (uncor.). It was recrystallized from methanol, m. p. 157-159" (uncor.) ; mixed melting point with L-arabinose unchanged. The initial specific rotation of a 2% aqueous solution of the material was +170 falling to $103. L-Arabinose has the specific equilibrium rotation 105.5. Precipitation with p-bromophenylhydrazine gave a 95% yield of almost pure L-arabinose p-bromo-phenylhydrazone, m. p. 152-154"; mixed melting point with authentic phenylhydrazone derivative unchanged. PORTLAND, OREGON RECEIVED MARCH17, 1949
+
The Preparation of the Perchlorates of Some Alkanolamin es
VOl. 71
The recrystallized salt was dried in an evacuated desiccator over phosphorus pentoxide. The dried salts were analyzed by the method of Arndt and Nachtwey.6 (6) Arndt and Nachtwey, ibid., 59B,446 (1926).
CHEMISTRY DIVISION,RESEARCH DEPARTMENT NAVALORDNANCE TESTSTATION INYOKERN, CALIFORNIA RECEIVED MARCH28, 1949 POSTOFFICE,CHINALAKE,CALIF.
Oxidation in Decarboxylation of Acids with Copper Chromite BY WILLIAMG. DAUBEN AND PETER COAD
It has been reported' that when phenylacetic acid labeled in the carboxyl group with C14 was decarboxylated over a copper chromite The preparation of the chlorides of several catalyst in quinoline at 20.5', the specific activity alkanolamines has been reported.2ss The usual of the evolved carbon dioxide was slightly less method was to pass anhydrous hydrogen chloride than that of the original acid. We have found into a solution of the alkanolamine in ether that this dilution of the radioactive carbon dioxide whereupon the desired salt precipitated. The is due to non-radioactive carbon dioxide formed present note concerns the preparation of the by the oxidation of the reaction product, toluene. perchlorates of some alkanolamines. The salts Methylene-labeled phenylacetic acid was preobtained were colorless, hygroscopic, crystalline pared from carboxyl-labeled benzoic acid in the solids. The fused salts showed a strong tendency conventional manner and decarboxylated under to supercool. various conditions. With commercial copper Experimental Part chromite catalyst2 at pot temperatures of 170, 8-Hydroxyethylamine (ethanolamine) was obtained 205 and 230') the evolved carbon dioxide confrom the Eastman Kodak Co. N,N-Diethyl-@-hydroxyethylamine, N,N-dimethyl-@-hydroxyethylamine and N- tained 0.07, 0.5 and 0.6y0,respectively, of the methyl-8-hydroxyethylamine were obtained from the C14 which was originally present in the methylene Carbide and Carbon Chemicals Corporation. These carbon atom. When copper chromite prepared amines were distilled at atmospheric pressure through a as described by Lazier3 was used a t 205', only 24-inch Vigreux column. The boiling ranges of the fractions used are shown by Table I. They agreed well 0.3%'04was found. This oxidation of the toluene formed in the with previously reported v a l ~ e s . * ~ * ~ ~ * ~ The salts were prepared by dissolving 2 g. of the amine reaction is most likely due to the cupric oxide in 30 ml. of absolute ethanol and adding the amount of present in the catalyst6 since it was found that 70% perchloric acid calculated to be sufficient t o neutralize when the copper chromite was reduced with the amine. Upon removal of the alcohol by evaporation hydrogen before use only 0.1% was found and under reduced pressure, a gummy residue remained. This residue could be obtained in crystalline form by when iron or copper powder was used no trace repeated washing with ether and slow cooling from the of radioactivity could be detected. fused state. However, purification was more easily It was also found that when /3-methyleneachieved by dissolving the gummy residue in 15 ml. of absolute ethanol, adding anhydrous ether un$l the solu- labeled-0-phenylpropionic acid, prepared from tion became cloudy, and cooling t o -10 . Crystals methylene-labeled phenylacetic acid, was deslowly formed, and after several hours a t this temperature carboxylated over copper chromite a t 230') the supernatant liquid was decanted and the crystalliza0.3% of the original C14 was evolved. It is tion repeated. interesting to note that Fries and Calvin6 obTABLE I tained similar results when methyl-labeled barium ~HYDROXYETHYLAMINE AND DERIVATIVES acetate was decarboxylated by pyrolysis. Thus, -Perchlorateit is recommended that copper powder rather B. p." Chlorine, OC. M. p.." % than copper chromite be used in decarboxylations Amine (760 mm.) OC. Calcd. Found in tracer work. ,¶-Hydroxyethylamine 170-171 131-132 21.8 21.7 BY R. D. CADLE,~ BETTY JANE ROBSON AND R. W. MOSHIER'
N-Methyl-,¶-hydroxyethylamine N,N-Dimethyl-B-hydroxyethylamine N,N-Diethyl-B-hydroxyethylamine 5
Corrected.
158
37.5-38.0 20.2 20.0
134
40.0-40.5 18.3 18.3b
160
49.5-50.5 15.9 16.1b
Two identical analyses.
(1) Present address: Stanford Research Institute, Stanford, California. (2) Horne and Shriner, THIS JOURNAL, 64, 2925 (1932). , 1069 (1898). (3) Knorr and Matthes, B c ~ .Si, (4) FrPnkel and Cornelius, ibid., 61, 1654 (1918). (5) Knocr, ibid., SO, 909 (1897).
Experimental Methylene-labeled Phenylacetic Acid.-Carboxyllabeled methyl benzoate (31.1 g., 0.229 mole, specific (1) Dauben, Reid, Yankwich and Calvin, THISJOURNAL, 68, 2117 (1946). (2) Copper Chromite Catalyst, No. Cu-186-powder, Harshaw Chemical Company, Cleveland, Ohio. (3) "Organic Syntheses," Coll. Vol. 11, John Wiley and Sons, Inc., New York, N.Y., p. 142 (1944). (4) All percentages refer to that originally present in the methylene carbon atom. (5) Stroupe, THIS JOURNAL, 71, 569 (1949). (6) Fries and Calvin, ibid., 70, 2235 (1948).
NOTES
Aug., 1949 activity X 8':3,300 cts./min./mg. barium carbonate) was reduced with 8.7 g. (0.228 mole) of lithium aluminum hydride following the procedure of Nystrom and Brown.* The benzyl alcohol was obtained in a yield of 21.1 g. (85.5'%), b. p. 114-115' (32 mm.). Methylene-labeled Benzyl Chloride.-In an all-glass apparatus closed with a calcium chloride tube, 10.3 g. (6.6 cc., 0.075 mole) of phosphorus trichloride was added to 21.1 g. (0.195 mole) of benzyl alcohol (prepared above) a t zero degrees. The mixture was allowed t o stand a t room temperature for thirty minutes and a t 50" for one hour. The excess DhosDhorus trichloride was removed and the benzyl chloiide histilled, b. p. 60-61' (12 mm.), yield 21.8 g. (88.lyO). Methylene-labeled Phenylacetic Acid.-Benzylmagnesium chloride was prepared from 21.8 g. (0.172 mole) of methylene-labeled-benzyl chloride and 4.2 g. (0.172 atomj of magnesium turnings. The Grignard reagent was carbonated a t -5" with gaseous carbon dioxide and the reaction mixture processed in the usual manner. The phenylacetic acid was recrystallized from petroleum ether, m. p. 76-77" (cor.), yield, 17.3 g. ( 7 4 7 0 ) specific ~ activity X 8:3,300 cts./min./mg. barium carbonate. p-Methylene-labeled 8-Phenethyl Alcohol.-Phenylacetic acid (11.1 g.) was reduced with lithium aluminum hydride as above and p-phenethyl alcohol was obtained in a yield of 8.5 g. (85.6y0), b. p. 114" (9 mm.). P-Methylene-labeled p-Phenethyl Chloride.-p-Phenethyl alcohol (8.5 9.) was allowed t o react with 4.8 g. of phosphorus trichloride in the normal manner and the chloride was received in a yield of 3.3 g. (33.8%), b. p. 55' (2 mm.). &Methylene-labeled ,%Phenylpropionic Acid.-& Phenethylmagnesium chloride was prepared from 3.3 g. of @-phenethylchloride (prepared above) and 0.63 g. of magnesium and the Grignard reagent carbonated with gaseous carbon dioxide, yield 1.82 g. (51.5%), m. p. 48-49', specific activity X 9:3,300 cts./min./mg. barium carbonate. Decarboxylation Procedure.-A mixture of 0.25 g. of the acid and 0.25 g. of the catalyst and 5 cc. of quinoline was heated for forty minutes in a salt-bath. The reaction mixture was flushed continuously with nitrogen and after the heating the aeration continued for one hour a t room temperature. The evolved carbon dioxide was collected i n 50 cc. of 0.14 M barium hydroxide. The barium carbonate was collected by filtration under nitrogen and the precipitate qtrashed with water, alcohol and ether and The yields varied from 4040%. dried a t 110 All samples of barium carbonate were regenerated t o carbon dioxide and reprecipitated t o check for radioactive impurities. In all cases, a constant specific activity was obtained. Radioactivity Determination.-The procedure of Dauben, Reid and YankwichO was employed for sample preparation and counting.
.
(7) This value was obtained by combustion of a microsample of the ester, precipitation of the carbon dioxide as barium carbonate and counting the barium carbonate. To correct for the dilution of activity in the compound, the ohserved specific activity was multiplied by eight. (8) Nystrom and Brown, ibid., 69, 1197 (1947). (9) Dauben, Reid and Yankwich, Anal. Chcm., 19, 828 (1947).
DEPARTMENT OF CHEMISTRY OF CALIFORNIA UNIVERSITY BERXELEY 4, CALIFORNIARECEIVEDFEBRUARY 17, 1949
Reaction of ThiophenealdehydeDerivatives with Maleic Anhydride BY WERNERH E R Z ~
The present note describes the reaction of two derivatives of 2-thiophenealdehyde with maleic (1) Present address: Department of Chemistry, University of Illinois, Urbana, Illinois.
2929
anhydride. Parallel reactions of benzylidene2 and f~rfurylidene~ derivatives have been reported previously. Experimental Thiophenealdehyde - 1-maleylphenylhydrazone .-A solution of 3 g. of thiophenealdehyde phenylhydrazone' in 20 ml. of ether was treated with 1.8 g. of maleic anhydride. The solution was warmed until solution of the anhydride occurred. The crude product which separated after standing overnight was washed with ether and weighed 4.5 g. Several recrystallizations fro? ethanol raised the m. p. of the yellow needles to 119-120 Anal. Calcd. for C1bH12N203S: C, 59.99; H, 4.03; neut. equiv., 300. Found: C, 59.95; H, 4.09; neut. equiv., 301. Under the same conditions pyrrolealdehyde phenylhydrazone on treatment with maleic anhydride yielded golden-yellow needles which decomposed immediately on exposure to air and could not be recrystallized satisfactorily. N-p-Tolylmaleamic Acid.-A solution of 1.8 g. of thiophenealdehyde #-toluidine6 in 15 ml. of ether on treatment with 1.2 g. of maleic anhydride gave yellowish-green needles, m. p. 201" with gas evolution after recrystallization from ethanol, which did not depress the m. p. of authentic N-p-tolylmaleamic acid.6
.
(2) La Parola, Gam. chim. ifal., 64, 919 (1934); 65, 624 (1935). (3) Herz, THISJOURNAL, 67, 1854 (1945). (4) Biedermann, Bcr., 19, 636 (1886). (5) Hantzsch and Witz, ibid., 36, 841 (1901). (6) Dunlap and Phelps, A m . Chcm. J . , 19, 492 (1897).
UNIVERSITY OF COLORADO BOULDER, COLORADO
RECEIVED APRIL8, 1949
The Heat Capacity of Organic Vapors. VI. Acetone' BY BEN T. COLLINS,~ CHARLES F. COLEMAN AND THOMAS DE VRIES
The work reported in this paper is a continuation of a program for measuring the heat capacity of organic vapors. The heat capacity and heat of vaporization of acetone has been measured a t 1 atm., a t temperatures from near its boiling point to 150'.
Experimental and Results Two sets of determinations are reported. Those of set I were made with a reverse-flow calorimeter and auxiliary equipment previously described3; those of set 11, with the apparatus and by the procedure described in the preceding paper.4 The values obtained for the heat capacity are presented in Table I and Fig. 1. The latter also shows the value 22.5 cal./mole/degree a t 137O, reported by Bennewitz and RossnerJSand a line drawn through the calculated values of C, a t 1 atm. by Dobratz.6 Other values reported in the literature are 20.1 and 21.7 for the temperature (1) Abstracted from the Ph.D. thesis of C. F. Coleman. (2) Present address: Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Mass. (3) De Vries and Collins, THISJOURNAL, 63, 1343 (1941). (4) Coleman and De Vries, ibid., 71, 2839 (1949). (5) Bennewitz and Rossner, Z . physik. Chcm., BS9, 125 (1938). (6) Dobratz. Ind. Enp. Chum., 33, 759 (1941).
